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CN102417454B - Cyclic olefin compound having photoreactive group and photoreactive polymer - Google Patents

Cyclic olefin compound having photoreactive group and photoreactive polymer Download PDF

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CN102417454B
CN102417454B CN201110296139.1A CN201110296139A CN102417454B CN 102417454 B CN102417454 B CN 102417454B CN 201110296139 A CN201110296139 A CN 201110296139A CN 102417454 B CN102417454 B CN 102417454B
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carbonatoms
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崔大胜
全成浩
元永喆
柳东雨
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LG Corp
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Abstract

Disclosed therein is a novel cyclic olefin compound having a photoreactive group and a novel photoreactive polymer. The cyclic olefin compound is applicable to various photoreactions, such as of liquid crystal alignment films and can be preferably used as a precursor of different organic compounds or polymers.

Description

Cyclic olefins and the photoreactive polymer with photoreactive group
Technical field
The present invention relates to a kind of Novel ring olefin(e) compound and photoreactive polymer with photoreactive group.More specifically, the present invention relates to a kind of precursor (precursor) that can be applicable to the various photoresponses fields such as liquid crystal orientation film and be preferably used as multiple organic compound or polymkeric substance, there is Novel ring olefin(e) compound and the photoreactive polymer prepared therefrom of photoreactive group.
Background technology
Recently, the various smooth Application Areass such as Thin Film Transistor-LCD (TFT-LCD) or photoresist material are used multiple photoreactive compound or polymkeric substance.
For example, in TFT-LCD, for liquid crystal is used to alignment films as photoswitch under liquid crystal layer, in these alignment films, use recently photoreactive polymer etc., to be suitable for the light orientation of utilizing UV.
Wherein, light orientation refers to that the photoreactive polymer functional group (photoreactive group) of regulation causes photoresponse under the UV effect that is rotated polarization, makes the main chain of polymkeric substance arrange towards certain orientation, so that the mechanism of liquid crystal aligning in this process.
Therefore, in order more effectively to carry out this light orientation, the photoreactive polymer that described alignment films comprises should with liquid crystal layer in molecule interact preferably, also to show excellent photoreactivity.
In addition, along with photoreactive compound or polymkeric substance are applied to more areas gradually, in fact need various photoreactive compounds or polymkeric substance, such as more kinds of light (as UV of the UV to different directions polarization or different wave length etc.) is shown to excellent photoreactivity.
Yet, the photoreactive polymer known in the past etc., mostly or can not show excellent photoreactivity, otherwise insufficient with the interaction of liquid crystal molecule.Especially, the exploitation that various light is shown to excellent photoreactive photoreactive polymer etc. is carried out abundant not.
Summary of the invention
In view of this, the invention provides a kind of various photoresponses fields such as liquid crystal orientation film that can be applicable to, and can be used as various organic compound or polymer precursor, there is the Novel ring olefin(e) compound of photoreactive group.
In addition, the invention provides a kind of photoreactive polymer, it is easy to regulate the photoreactivity to various light, and for alignment films etc., can show that interaction with liquid crystal molecule increases and photoreactivity is excellent.
The present invention also provides a kind of alignment films that comprises described photoreactive polymer.
The invention provides a kind of cyclic olefins with the photoreactive group being represented by following Chemical formula 1.
[Chemical formula 1]
In described Chemical formula 1,
Q is 0 to 4 integer,
At least one in R1, R2, R3 and R4 group that following Chemical formula 1 a represents of serving as reasons,
Except the group being represented by Chemical formula 1 a, remaining R1 to R4 is identical or different, and respectively independently selected from hydrogen; Halogen; Substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkenyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkynyl; Substituted or unsubstituted carbonatoms is 3～12 cycloalkyl; Substituted or unsubstituted carbonatoms is 6～40 aryl; Substituted or unsubstituted carbonatoms is 5～12 aralkyl; And comprise at least one the polar functional group being selected from oxygen, nitrogen phosphate and sulfur, silicon and boron,
When described R1～R4 is not hydrogen, halogen or polar functional group, R1 and R2 in conjunction with or at least one combination of R3 and R4 combination interconnect and to form carbonatoms be 1～10 alkylidene group or R1 or R2 is connected with any one in R3 and R4 that to form carbonatoms be the aromatic ring that 4～12 saturated or unsaturated fatty acids ring or formation carbonatoms are 6～24
[Chemical formula 1 a]
In described Chemical formula 1 a,
A be selected from alkylidene group that oxygen, sulphur ,-NH-, substituted or unsubstituted carbonatoms are 1～20, carbonyl ,-(O=) C-O-,-O-C (=O)-,-CONH-and the substituted or unsubstituted carbonatoms arylidene that is 6～40,
B is singly-bound, oxygen, sulphur ,-NH-or Isosorbide-5-Nitrae-phenylene,
R9 is selected from the alkynylene that sub-aralkyl that the cycloalkylidene that the alkylidene group that singly-bound, substituted or unsubstituted carbonatoms are 1～20, the alkylene group that substituted or unsubstituted carbonatoms is 2～20, substituted or unsubstituted carbonatoms are 3～12, the arylidene that substituted or unsubstituted carbonatoms is 6～40, substituted or unsubstituted carbonatoms are 7～15 and substituted or unsubstituted carbonatoms are 2～20
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～40; The sub-aralkyl that the carbonatoms that is not substituted or is selected from least one functional group's replacement in halogen, cyano group and nitro is 7～15; Or the inferior heteroaryl (hetero arylene) that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40,
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～40; Or the inferior heteroaryl that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40,
R10 is selected from hydrogen; Halogen; Cyano group; Nitro;-NCS; Substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkyl; Substituted or unsubstituted carbonatoms is 1～20 alkoxyl group; Substituted or unsubstituted carbonatoms is 6～30 aryloxy; And the substituted or unsubstituted carbonatoms aryl that is 6～40.
In addition, the invention provides a kind of photoreactive polymer that comprises the repeating unit being represented by following Chemical formula 2 a or 2b.
In described Chemical formula 2 a and 2b, m is 50～5000, q, R1, R2 independently respectively, and R3 and R4 define as Chemical formula 1.
The present invention also provides a kind of alignment films that comprises described photoreactive polymer.
In addition, the invention provides the liquid crystal retardation film (Retardation film) that comprises described alignment films and be positioned at the liquid crystal layer in this alignment films.
The present invention also provides the indicating meter that comprises described alignment films.
According to the structure of Chemical formula 1 a, cyclic olefins of the present invention can have as photoreactive group such as laurate structure or cinnamophenone structures (chalcone).Therefore, himself show excellent photoreactivity, thereby can be applicable to the various photoresponses fields such as liquid crystal orientation film, and preferably can be used as the precursor of other various organic compound or polymkeric substance.
In addition, described cyclic olefins can have further by aromatic ring the photoreactive group replacing, for example laurate structure or cinnamophenone structure.Conventionally liquid crystal molecule has aromatic ring, due to aromatic ring as further substituting group, this cyclic olefins or photoreactive polymer prepared therefrom can show with the interaction of liquid crystal molecule and increase, and therefore can more effectively carry out light orientation.
Furthermore, the structure of Chemical formula 1 a that can be by cyclic olefins described in modification shows excellent photoreactive multiple photoreactive compound or polymkeric substance etc. to provide to various dissimilar light.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of conventional alignment films exemplary configurations.
Embodiment
Below, describe in detail according to the cyclic olefins with photoreactive group, photoreactive polymer and the alignment films etc. of the embodiment of the present invention.
According to a preferred embodiment of the invention, provide the cyclic olefins with the photoreactive group being represented by following Chemical formula 1.
[Chemical formula 1]
In described Chemical formula 1,
Q is 0～4 integer,
At least one in R1, R2, R3 and R4 is the group being represented by following Chemical formula 1 a,
Except the group being represented by Chemical formula 1 a, remaining R1～R4 is identical or different, and respectively independently selected from hydrogen; Halogen; Substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkenyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkynyl; Substituted or unsubstituted carbonatoms is 3～12 cycloalkyl; Substituted or unsubstituted carbonatoms is 6～40 aryl; Substituted or unsubstituted carbonatoms is 5～12 aralkyl; And comprise at least one the polar functional group being selected from oxygen, nitrogen phosphate and sulfur, silicon and boron,
When described R1～R4 is not hydrogen; Halogen; Or during polar functional group, R1 and R2 in conjunction with or at least one combination of R3 and R4 combination to interconnect and form carbonatoms be 1～10 alkylidene group, or R1 or R2 are connected with any one in R3, R4 and to form carbonatoms be 4～12 saturated or unsaturated fatty acids ring or form the aromatic ring that carbonatoms is 6～24
[Chemical formula 1 a]
In described Chemical formula 1 a,
A be selected from alkylidene group that oxygen, sulphur ,-NH-, substituted or unsubstituted carbonatoms are 1～20, carbonyl ,-(O=) C-O-,-O-C (=O)-,-CONH-and the substituted or unsubstituted carbonatoms arylidene that is 6～40,
B is singly-bound, oxygen, sulphur ,-NH-or Isosorbide-5-Nitrae-phenylene,
R9 is selected from the alkynylene that sub-aralkyl that the cycloalkylidene that the alkylidene group that singly-bound, substituted or unsubstituted carbonatoms are 1～20, the alkylene group that substituted or unsubstituted carbonatoms is 2～20, substituted or unsubstituted carbonatoms are 3～12, the arylidene that substituted or unsubstituted carbonatoms is 6～40, substituted or unsubstituted carbonatoms are 7～15 and substituted or unsubstituted carbonatoms are 2～20
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～40; The sub-aralkyl that the carbonatoms that is not substituted or is selected from least one functional group's replacement in halogen, cyano group and nitro is 7～15; Or the inferior heteroaryl that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40,
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～40; Or the inferior heteroaryl that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40,
R10 is selected from hydrogen; Halogen; Cyano group; Nitro;-NCS; Substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkyl; Substituted or unsubstituted carbonatoms is 1～20 alkoxyl group; Substituted or unsubstituted carbonatoms is 6～30 aryloxy; And the substituted or unsubstituted carbonatoms aryl that is 6～40.
This compound can have wherein have been introduced photoreactive group (Chemical formula 1 is the cycloolefin structure of (as laurate structure or cinnamophenone structure) a), and described cycloolefin structure can be used as the precursor of different compounds or the monomer of polymkeric substance.Owing to having this chemical structure of photoreactive group, the cyclic olefins that described Chemical formula 1 represents itself can be used as photoreactive compound.
In addition, owing to can be used as the characteristic of the cyclic olefins structure of precursor etc., by described compound, can prepare various compounds or polymkeric substance, so the compound of preparation or polymkeric substance are also because described photoreactive group can show excellent photoreactivity.Therefore, utilize described cyclic olefins, can prepare and be applicable to the multiple photoreactive compound of various smooth Application Areass or polymkeric substance etc.
And described cyclic olefins can have following structure: aromatic ring substituting group wherein by the further key of particular functional group A, link as in the photoreactive group such as laurate structure or cinnamophenone structure.Conventionally liquid crystal molecule has aromatic ring, and because other key is linked the aromatic ring substituting group in described cyclic olefins this cyclic olefins or thus obtained photoreactive polymer can show with the interaction of liquid crystal molecule and increase, and therefore can more effectively carry out light orientation.Therefore, described cyclic olefins and thus obtained photoreactive polymer are preferred for liquid crystal orientation film etc., can show with the interaction of liquid crystal molecule and increase and photoreactivity excellence.
Furthermore, use the structure of the Chemical formula 1 a of cyclic olefins described in different arylidene or inferior heteroaryl (heteroarylene) modification, especially described further aromatic ring substituting group type, thereby be easy to regulate the photoreactivity of described cyclic olefins and thus obtained photoreactive polymer.Therefore, by this cyclic olefins, can obtain different light is shown to excellent photoreactive multiple photoreactive compound or polymkeric substance etc.
Below, described cyclic olefins and thus obtained photoreactive polymer etc. are more specifically described.
In described cyclic olefins, as the upper substituent polar functional group of described R1～R4 (comprising at least one the polar functional group being selected from oxygen, nitrogen phosphate and sulfur, silicon and boron), can be selected from following functional group, can be also to comprise at least one the polar functional group being selected from oxygen, nitrogen phosphate and sulfur, silicon or boron in addition.
-OR 6、-OC(O)OR 6、-R 5OC(O)OR 6、-C(O)OR 6、-R 5C(O)OR 6、-C(O)R 6、-R 5C(O)R 6、-OC(O)R 6、-R 5OC(O)R 6、-(R 5O) p-OR 6、-(OR 5) p-OR 6、-C(O)-O-C(O)R 6、-R 5C(O)-O-C(O)R 6、-SR 6、-R 5SR 6、-SSR 6、-R 5SSR 6、-S(＝O)R 6、-R 5S(＝O)R 6、-R 5C(＝S)R 6-、-R 5C(＝S)SR 6、-R 5SO 3R 6、-SO 3R 6、-R 5N＝C＝S、-N＝C＝S、-NCO、-R 5-NCO、-CN、-R 5CN、-NNC(＝S)R 6、-R 5NNC(＝S)R 6、-NO 2、-R 5NO 2、
And
In this polar functional group, p is respectively 1～10 integer independently, and R5 is that substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkylidene group; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkylene group; Unsubstituted carbonatoms is 2～20 straight or branched type alkynylene; Substituted or unsubstituted carbonatoms is 3～12 cycloalkylidene; Substituted or unsubstituted carbonatoms is 6～40 arylidene; Substituted or unsubstituted carbonatoms is 1～20 sub-carbonyl oxygen base; Or the alkylene oxide group that substituted or unsubstituted carbonatoms is 1～20,
R6, R7 and R8 are respectively independently selected from hydrogen; Halogen; Substituted or unsubstituted carbonatoms is 1～20 straight or branched type alkyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkenyl; Substituted or unsubstituted carbonatoms is 2～20 straight or branched type alkynyl; Substituted or unsubstituted carbonatoms is 3～12 cycloalkyl; Substituted or unsubstituted carbonatoms is 6～40 aryl; Substituted or unsubstituted carbonatoms is 1～20 alkoxyl group; And the substituted or unsubstituted carbonatoms carbonyl oxygen base that is 1～20.
In addition, in described cyclic olefins, described in can be (not for example to be substituted or to be selected from arylidene that carbonatoms that at least one functional group in halogen, cyano group and nitro replaces is 6～40, substituted or unsubstituted phenylene or 1,4-or 2,6-naphthylidene (naphthalene) etc.); The sub-aralkyl that the carbonatoms that is not substituted or is selected from least one functional group's replacement in halogen, cyano group and nitro is 7～15; Or the inferior heteroaryl that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40 (for example, and the sub-thienyl of 2,5-(2,5-thiophenediyl), 2,5-furylidene (2,5-furanylene) etc.).
And, described in linking by particular functional group A key on can be not to be substituted or to be selected from the arylidene that carbonatoms that at least one functional group in halogen, cyano group and nitro replaces is 6～40 (for example, substituted or unsubstituted phenylene or Isosorbide-5-Nitrae-or 2,6-naphthylidene etc.); Or the inferior heteroaryl that the carbonatoms that comprises 14 family, the assorted element of Huo 16 families of 15 family is 4～40 (for example, and the sub-thienyl of 2,5-(2,5-thiophenediyl), 2,5-furylidene (2,5-furanylene) etc.).
On the other hand, in the structure of above-mentioned cyclic olefins, each substituent definition is specific as follows:
First, " alkyl " represents that carbonatoms is 1～20, is preferably 1～10, more preferably the saturated monovalence hydrocarbon of the straight or branched type part of 1～6.Alkyl not only represents unsubstituted group, can also represent the group further being replaced by the specific substituting group of aftermentioned.As alkyl, can exemplified by methyl, ethyl, propyl group, 2-propyl group, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, dodecyl, methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, brooethyl etc.
" thiazolinyl " represents to comprise 1 above carbon-to-carbon double bond and carbonatoms is 2～20, is preferably 2～10, more preferably the straight or branched type monovalence hydrocarbon part of 2～6.Thiazolinyl can be by comprising carbon-to-carbon double bond carbon atom or saturated carbon atom combination.Thiazolinyl not only represents unsubstituted group, can also represent the group further being replaced by the specific substituting group of aftermentioned.As thiazolinyl, can exemplified by vinyl, 1-propenyl, 2-propenyl, crotyl, 3-butenyl, pentenyl, 5-hexenyl, laurylene base etc.
" cycloalkyl " represents to have the saturated or monocyclic, bicyclic or tricyclic hydrocarbon part of unsaturated non-aromatic monovalence of 3～12 ring carbon, also can represent the group further being replaced by the specific substituting group of aftermentioned.For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, suberyl, ring octyl group, decahydro naphthyl, adamantyl (adamantyl), norcamphyl (NORBORNYL, that is, and dicyclo [2,2,1] heptan-5-thiazolinyl) etc.
" aryl " represents to have 6～40, preferably has the monocyclic, bicyclic or tricyclic aromatic hydrocarbon part of monovalence of 6～12 annular atomses, also comprises the group that expression is further replaced by the specific substituting group of aftermentioned.As aryl, can exemplified by phenyl, naphthyl and fluorenyl etc.
" alkoxy aryl " represents the group that in the above-mentioned aryl being defined, at least one hydrogen atom alkoxy replaces.As alkoxy aryl, can exemplify p-methoxy-phenyl, ethoxyl phenenyl, propoxy-phenyl, butoxy phenyl, pentyloxy phenyl, hexyloxy phenyl, heptyloxybenzene base, octyloxyphenyl, ninth of the ten Heavenly Stems oxygen base phenyl, methoxyl group phenylbenzene, methoxyl group naphthyl, methoxyl group fluorenyl or methoxyl group anthryl (anthracenyl) etc.
" aralkyl " represents the group that in the above-mentioned alkyl being defined, at least one hydrogen atom is replaced by aryl, can also represent the group further being replaced by the specific substituting group of aftermentioned.Such as benzyl, diphenyl-methyl (Benzhydry) and trityl (trityl) etc.
" alkynyl " represents to comprise at least one carbon-to-carbon triple bond and carbonatoms is 2～20, is preferably 2～10, more preferably the monovalence hydrocarbon part of the straight or branched type of 2～6.The carbon atom of alkynyl by comprising carbon-to-carbon triple bond or saturated carbon atom combination.Alkynyl can also represent the group further being replaced by the specific substituting group of aftermentioned.Such as ethynyl and proyl etc.
" alkylidene group " represents that carbonatoms is 1～20, is preferably 1～10, more preferably the saturated divalence hydrocarbon of the straight or branched type part of 1～6.Alkylidene group can also comprise the group that expression is further replaced by the specific substituting group of aftermentioned.As alkylidene group, can exemplify methylene radical, ethylidene, propylidene, butylidene, hexylidene etc.
" alkylene group " represents to comprise more than one carbon-to-carbon double bond and carbonatoms is 2～20, is preferably 2～10, more preferably the straight or branched type divalence hydrocarbon part of 2～6.Alkylene group can be by comprising carbon-to-carbon double bond carbon atom and/or saturated carbon atom combination.Alkylene group can also comprise the group that expression is further replaced by the specific substituting group of aftermentioned.
" cycloalkylidene " representative ring carbon is the saturated or monocyclic, bicyclic or tricyclic hydrocarbon part of unsaturated non-aromatic divalence of 3～12, can also represent the group further being replaced by the specific substituting group of aftermentioned.Such as cyclopropylene, cyclobutene (cyclo butylene) etc.
" arylidene " has 6～20, preferably has the monocyclic, bicyclic or tricyclic aromatic hydrocarbon part of divalence of 6～12 annular atomses, can also represent the group further being replaced by the specific substituting group of aftermentioned.Aromatics part only comprises carbon atom.As arylidene, can exemplify phenylene etc.
" sub-aralkyl (aralkylene) " represents the divalent moiety that in alkyl defined above, at least one hydrogen atom is replaced by aryl, can also represent the group further being replaced by the specific substituting group of aftermentioned.Can exemplify benzylidene etc.
" alkynylene (alkynylene) " represents to comprise at least one carbon-to-carbon triple bond and carbonatoms is 2～20, is preferably 2～10, more preferably the straight or branched type divalence hydrocarbon part of 2～6.Alkynylene can be by comprising carbon-to-carbon triple bond carbon atom or saturated carbon atom combination.Alkynylene can also represent the group further being replaced by the specific substituting group of aftermentioned.Such as ethynylene or sub-propine (propynylene) etc.
So-called substituting group described above " is substituted or is not substituted " and refer to and not only comprises these each substituting groups itself, also comprises the group further being replaced by specific substituting group.In this manual, as can further replacing each substituent substituting group, can exemplify halogen, alkyl, thiazolinyl, alkynyl, haloalkyl, haloalkenyl group, halo alkynyl, aryl, halogenated aryl, aralkyl, halo aralkyl, alkoxyl group, halogenated alkoxy, carbonyl oxygen base, halo carbonyl oxygen base, aryloxy, halo aryloxy, silyl (silyl), siloxy-or " polar functional group that comprises oxygen, nitrogen phosphate and sulfur, silicon or boron " as above etc.
Above-mentioned cyclic olefins can be according to following ordinary method preparation.That is, cycloolefin is for example introduced predetermined substituting group in norbornylene compounds, more specifically introduces photoreactive group being represented by Chemical formula 1 a etc.For example, by making the norborneol enols (norbornene alkylol) such as norbornylene methyl alcohol (norbornene methanol) carry out condensation reaction corresponding to the carboxylic acid cpd of the photoreactive group of Chemical formula 1 a or chloride compounds and make described cyclic olefins with having, and structure and the kind of the photoreactive group that can be represented by Chemical formula 1 a according to other, by the whole bag of tricks, introduce described photoreactive group and prepare above-mentioned cyclic olefins.
On the other hand, according to another embodiment of the present invention, provide the photoreactive polymer that comprises the repeating unit being represented by following Chemical formula 2 a or 2b.
[Chemical formula 2 a] [Chemical formula 2 b]
In described Chemical formula 2 a and 2b, m is 50～5000, q, R1, R2 independently respectively, and R3 and R4 define as Chemical formula 1.
This photoreactive polymer comprises the repeating unit being derived by above-mentioned cyclic olefins, can show excellent photoreactivity, and owing to having the structure of Chemical formula 1 a, especially has the aromatic ring substituting group connecting by the further key of particular functional group A can show with the interaction of liquid crystal molecule and increase, and photoreactivity is excellent.In addition, in different arylidene or inferior heteroaryl, selection and modified aromatic ring substituents can show excellent photoreactivity to various light.
In addition, described photoreactive polymer comprises the norbornylene class repeating unit being represented by Chemical formula 2 a or 2b as main repeating unit.The structure comparatively robust of this norbornylene class repeating unit, the photoreactive polymer that comprises this repeating unit is because glass transition temperature (Tg) is higher, be about more than 300 ℃, preferably be about 300～350 ℃, therefore compare with photoreactive polymer in the past etc., can show excellent thermostability.And described photoreactive polymer is combined with photoreactive group at described norbornylene class repeating unit, because this structural performance photoreactive group can more freely move in high polymer main chain, therefore can show excellent orientation.
Therefore, described photoreactive polymer can be used for, on the liquid crystal aligning layer of light orientation, also can be used for other various smooth Application Areass.
About being combined in each substituent definition of described photoreactive polymer, Chemical formula 1 was carried out to detailed description, do not repeat them here.
And described photoreactive polymer can only comprise at least one repeating unit selecting in the repeating unit that free Chemical formula 2 a or 2b represent, but can be also the polymkeric substance that further comprises other kind repeating units.As this repeating unit, can exemplify any olefines repeating unit that is combined with or is not combined with cinnamate derivative, chalcones or azo photoreactive group; Esters of acrylic acid repeating unit or cyclenes hydro carbons repeating unit.The example of this repeating unit is disclosed in No. 2010-0021751st, Korean Patent Publication.
Just, described photoreactive polymer can comprise and be about more than 50 % by mole, is specifically about 50～100 % by mole, be preferably about 70 % by mole above, the repeating unit being represented by described Chemical formula 2 a or 2b, to prevent the excellent photoreactive variation of described Chemical formula 2 a or 2b.
In addition, form the Chemical formula 2 a of described photoreactive polymer or the repeating unit that 2b represents, can have and be about 50～5,000 the polymerization degree, is preferably about 100～4,000 the polymerization degree, is more preferably and is about 1,000～3,000 the polymerization degree.And described photoreactive polymer can have 10,000～100,0000, be preferably 20,000～500,000 weight-average molecular weight.Thus, be used to form while suitably comprising described photoreactive polymer in the coating composition of alignment films, show excellent coating, and the alignment films forming thus can show excellent liquid crystal aligning etc.
At wavelength, be about under the exposure of polarized light of 150～450nm, above-mentioned photoreactive polymer can show photoreactivity, for example, at wavelength, be about 200～400nm, is more specifically about under the exposure of polarized light of 250～350nm, can show photoreactivity.Especially, the aromatic ring substituting group connecting by the arylidene different or the further key of the particular functional group A in inferior heteroaryl selection or modification make the polarized light of the wider light of above-mentioned wavelength band and different directions can show excellent photoreactivity.
On the other hand, according to another embodiment of the present invention, provide the preparation method of described photoreactive polymer.This preparation method's a example, comprises step: exist and comprise under the condition that contains the 10th pre-catalyst of group 4 transition metal and the catalyst composition of promotor, the monomer that addition polymerization is represented by described Chemical formula 1.
[Chemical formula 1]
In described Chemical formula 1, q, R1, R2, R3 and R4 define as Chemical formula 2 a.
Now, described polyreaction can be carried out at the temperature of 10 ℃～200 ℃.If described temperature of reaction, lower than 10 ℃, can reduce polymerization activity, if higher than 200 ℃, can make catalyst decomposes, therefore inadvisable.
In addition, described promotor can comprise at least one being selected from the first promotor and the second promotor, and described the first promotor provides the Lewis base that can carry out with the metal of described pre-catalyst weak property coordination bonding; Described the second promotor provides the compound that comprises 15 family electron donor ligand.Preferably, described promotor can be the catalyst mixture that comprises the first promotor and the second promotor, wherein said the first promotor provides described Lewis base, and described the second promotor is for comprising selectively the compound of neutral 15 family electron donor ligand.
Now, the pre-catalyst based on 1 mole, comprises first promotor and 1～1 of 1～1,000 mole in described catalyst mixture, second promotor of 000 mole.If the content of the first promotor or the second promotor is too small, likely cannot normally bring into play the activity of catalyzer.Otherwise, if can reduce the activity of catalyzer on the contrary too greatly.
In addition, the described pre-catalyst that comprises the 10th group 4 transition metal can be used to have and be easy to participate in Lewis acid-alkali reaction, thereby the compound of the Lewis base functional group being departed from by central metal, makes this pre-catalyst by providing the easy separation of the first promotor of Lewis base to make central transition metal become catalyst activity kind (active species).For example, the example of pre-catalyst has allyl palladium chloride dipolymer ([(Allyl) Pd (Cl)] 2), palladium ((CH 3cO 2) 2pd)], palladium acetylacetonate ([CH 3cOCH=C (O-) CH 3] 2pd), NiBr (NP (CH 3) 3) 4, [PdCl (NB) O (CH 3)] 2deng.
In addition, as described the first promotor that the Lewis base that can carry out with the metal of pre-catalyst weak property coordination bonding is provided, can use be easy to form with Lewis base reaction transition metal room and with transistion metal compound carry out weak property coordination bonding with stablize generation like this transition metal compound or the compound of this compound is provided.The example of described the first promotor can comprise borine (as: B (C 6f 5) 3deng), borate (as: dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethyl ammonium tetrakis (penta fluoro phenyl) borate) etc.), aluminum alkyls (methylaluminoxane (MAO) or Al (C 2h 5) 3deng) or transition metal halide (AgSbF 6deng) etc.
In addition, described the second promotor as providing containing the compound of neutral 15 family electron donor ligand, can be used alkylphosphines, cycloalkyl phosphine or Phenylphosphine etc.
In addition, can use separately described the first promotor and the second promotor, also two kinds of promotors can be used to the single salt compound forming as making the compound of catalyst activation together.For example, can use alkylphosphines and borine or borate (borate) compound ions in conjunction with and the compound that forms etc.
By above-mentioned method, the photoreactive polymer of the embodiment that can prepare the repeating unit being represented by Chemical formula 2 a and comprise this repeating unit.Furthermore, when described photoreactive polymer comprises olefines repeating unit, cyclenes hydro carbons repeating unit or esters of acrylic acid repeating unit etc., conventional preparation method by each repeating unit forms these repeating units, and obtains described photoreactive polymer with the repeating unit copolymerization being represented by Chemical formula 2 a of preparing by aforesaid method.
On the other hand, when photoreactive polymer comprises the repeating unit being represented by Chemical formula 2 b, can make according to another embodiment of described preparation method.The preparation method of this another embodiment, comprise step: have to comprise under the condition that contains the 4th family, the 6th family or the 8th pre-catalyst of group 4 transition metal and the catalyst composition of promotor the monomer that ring-opening polymerization is represented by Chemical formula 1 and form the repeating unit being represented by Chemical formula 2 b.As alternative additive method, the photoreactive polymer that comprises the repeating unit being represented by described Chemical formula 2 b also can be made by the following method.; existence comprises under the condition that contains the 4th family, the 6th family or the 8th pre-catalyst of group 4 transition metal and the catalyst composition of promotor; the norborneol enols such as norbornylene methyl alcohol of take form the ring-opening polymerization polymer with five square rings as monomer ring-opening polymerization, introduce photoreactive group afterwards in this ring-opening polymerization polymer.Now, the introducing of described photoreactive group can be undertaken by following reaction.That is, make described ring-opening polymerization polymer and the carboxylic acid cpd or the chloride compounds that have corresponding to the photoreactive group of Chemical formula 1 a carry out polyreaction.
In described ring-opening polymerization step, if the two keys in the norbornylene ring that the monomers such as described Chemical formula 1 comprise are by hydrogenation, can carry out open loop, meanwhile carry out polymerization and make by the repeating unit of the expressions such as described Chemical formula 2 b and the photoreactive polymer that comprises this repeating unit.
Described ring-opening polymerization can be carried out under the catalyst mixture that comprises following component exists.That is the pre-catalyst that, comprises the 4th family (for example Ti, Zr, Hf), Huo 8 families of the 6th family (for example Mo, W) (for example Ru, Os) transition metal; The promotor that can carry out with the metal of described pre-catalyst the Lewis base that weak coordination bond closes is provided; And can strengthen selectively described pre-catalyst metal active containing the activator (activator) of the neutral 15 Ji of family 16 family's elements etc.And, under the existence of this catalyst mixture, with respect to monomer, add the linear alpha-olefins (linear alkene) such as 1-alkene, 2-alkene of the adjustable molecular size range of 1～100mol%, and carry out polymerization at 10 ℃～200 ℃ temperature, and with respect to monomer, add the catalyzer of Huo 8 families～10 family of Han 4 families (for example Ti, Zr) (for example Ru, Ni, Pd) transition metal of 1～30 % by weight, and carry out the reaction to the double-bond hydrogenation in norbornylene ring at 10 ℃～250 ℃ temperature.
When described temperature of reaction is too low, polymerization activity can be reduced, and catalyst decomposes can be made when too high, therefore inadvisable.And described hydrogen adds temperature of reaction when too low, the activity of hydrogenation reaction can be reduced, and catalyst decomposes can be made when too high, therefore inadvisable.
Han 4 families (for example Ti, Zr, Hf) of described catalyst mixture with respect to 1 mole, the pre-catalyst of Huo 8 families of the 6th family (for example Mo, W) (for example Ru, Os) transition metal, 1～100,000 mole provide is provided and can carries out with the metal of described pre-catalyst the promotor of the Lewis base that weak coordination bond closes; And the activator (activator) containing the neutral 15 Ji of family 16 family's elements that can strengthen selectively pre-catalyst metal active of 1～100 mole.
The content of described promotor is during lower than 1 mole, and catalyzer can lose activity, and content is during higher than 100,000 moles, can reduce the activity of catalyzer, therefore inadvisable.According to the kind of pre-catalyst, or without using described activator.The content of activator is during lower than 1 mole, and catalyzer can lose activity, and during higher than 100 moles, can reduce molecular weight, therefore inadvisable.
(be for example used for Han 4 families of hydrogenation reaction, Ti, Zr) Huo 8 Zhi of family 10 families (for example, Ru, Ni, Pd) catalyst content of transition metal, with respect to monomer during lower than 1 % by weight, can cause hydrogenation reaction insufficient, and can make polymkeric substance variable color during higher than 30 % by weight, therefore inadvisable.
Containing described the 4th family (for example, Ti, Zr, Hf), the pre-catalyst of Huo 8 families of the 6th family (for example, Mo, W) (for example, Ru, Os) transition metal, can use and there is the functional group that is easy to participate in Lewis acid-alkali reaction and departed from by central metal, as TiCl 4, WCl 6, MoCl 5or RuCl 3and ZrCl 4deng transistion metal compound, lewis acidic promotor is easily separated makes central transition metal become catalyst activity kind by providing to make this catalyzer.
In addition, provide the promotor of the Lewis base that can carry out with the metal of described pre-catalyst weak property coordination bonding, can use B (C 6f 5) 3deng borine or borate, methylaluminoxane (MAO) or Al (C 2h 5) 3, Al (CH 3) Cl 2deng aluminum alkyls (alkylaluminum), aluminum halide (aluminum halide), alkyl aluminum halide (alkylaluminum halide).Or aluminium can be used lithium (lithium), magnesium (magnesium), germanium (germanium), lead, zinc, tin, silicon etc. to replace.As mentioned above, promotor for be easy to form the room of transition metal with Lewis base reaction and carry out with transistion metal compound a little less than property coordination bonding with stablize generation like this transition metal compound or the compound of this compound is provided.
Although can add polymerization activator, also can not use according to the kind of pre-catalyst.Can strengthen described pre-catalyst metal active, activator (activator) containing the neutral 15 Ji of family 16 family's elements has, water, methyl alcohol, ethanol, Virahol, phenylcarbinol, phenol, sulfur alcohol (ethylmercaptan), ethylene chlorhydrin, Trimethylamine 99, triethylamine, pyridine (pyridine), oxyethane (ethylene oxide), benzoyl peroxide (benzoyl peroxide), tert-butyl peroxide (t-butyl peroxide) etc.
(be for example used for Han 4 families of hydrogenation reaction, Ti, Zr) Huo 8 families～10 family is (for example, Ru, Ni, Pd) catalyzer of transition metal is for can being at once dissolved in homogeneous (homogeneous) shape of solvent, or described metal complex catalyst is carried on the catalyzer on particulate carrier.Described particulate carrier is preferably silicon-dioxide, titanium dioxide, silicon-dioxide/chromic oxide (Chromia), silicon-dioxide/chromic oxide/titanium dioxide, silica/alumina, phosphaljel, silanized silica (silanized silica), silicone-hydrogel, the de-clay of illiteracy or zeolite.
The photoreactive polymer of the repeating unit that can be represented by Chemical formula 2 b by above-mentioned method preparation and an embodiment that comprises this repeating unit.And, when described photoreactive polymer comprises olefines repeating unit, cyclenes hydro carbons repeating unit or esters of acrylic acid repeating unit etc., also can form these repeating units by the conventional preparation method of each repeating unit, and obtain described photoreactive polymer with the repeating unit copolymerization being represented by Chemical formula 2 a of preparing by aforesaid method.
On the other hand, according to another embodiment of the present invention, provide a kind of alignment films that comprises above-mentioned photoreactive polymer.These alignment films, except comprising form of film, can also comprise the alignment films of film (film) form.According to another embodiment of the present invention, provide a kind of liquid crystal retardation film that comprises these alignment films and be positioned at the liquid crystal layer in this alignment films.
These alignment films and liquid crystal retardation film be except comprising above-mentioned photoreactive polymer as light orientated polymer, can utilize in this area known constituent and preparation method to make.
For example, described alignment films can form by the following method.That is, described photoreactive polymer, adhesive resin and light trigger mixed and be dissolved in organic solvent and obtain after coating composition, this coating composition is coated on substrate, and carrying out UV and solidify.
Now, described adhesive resin can be used acrylic resin, more specifically can use pentaerythritol triacrylate, dipentaerythritol acrylate, Viscoat 295, three (2-acrylyl oxy-ethyl) isocyanuric acid ester etc.
In addition, described light trigger can be used the conventional light trigger that can be used in alignment films without restriction, for example, can use the light trigger of known commodity Irgacure 907,819 by name.
And described organic solvent can be used toluene, methyl-phenoxide, chlorobenzene, ethylene dichloride, hexanaphthene, pentamethylene, 1-Methoxy-2-propyl acetate etc.Above-mentioned photoreactivity norbornylene analog copolymer shows excellent solubleness to various organic solvents, therefore in addition can also be not particularly limited and use various organic solvents.
In described coating composition, the solid concentration that comprises described photoreactive polymer, adhesive resin and light trigger can be 1～15wt%, and in order to become described alignment films to be preferably 10～15wt% with film forms casting (casting), and in order to form and to be preferably 1～5wt% with form of film.
As shown in Figure 1, the alignment films so forming can be formed on substrate, and is formed on below liquid crystal and plays the liquid crystal aligning effect that makes.Now, the substrate that described substrate can use the substrate that comprises cyclic polymer, the substrate that comprises propene polymer or comprise cellulose polymer compound etc., and can be coated with by scraper, rotary coating, the several different methods such as scraper plate coating, described coating composition is coated on substrate, carries out afterwards UV and be solidified to form alignment films.
In described UV solidification process, may there is light orientation, can illumination wavelength scope in this step be about the polarization UV of 150～450nm, to carry out orientation process.Now, exposure intensity is about 50mJ/cm 2～10J/cm 2, be preferably about 500mJ/cm 2～5J/cm 2.
UV as the applicable polarization of described UV, this polarization UV is selected from and is undertaken in the UV of polarization manipulation by UV being seen through or reflect in the method for following three kinds of devices, is coated with the polarizing appliance of the substrate of dielectric anisotropy material on 1. utilizing at silica glass, soda-lime glass, without transparency carrier surfaces such as soda-lime glasss; 2. precision deposits the Polarizer of aluminium or metal wire; Or Brewster (Brewster) polarizing appliance 3. reflecting based on silica glass etc.
Substrate temperature while irradiating described UV is preferably room temperature.But, according to circumstances in the temperature range below 100 ℃, under the heated state of substrate, can irradiate UV.By the formed final coating of a series of processes as above, its thickness is preferably 30～1000nm.
By aforesaid method, form alignment films, and form liquid crystal layer in the above, can make liquid crystal retardation film with ordinary method whereby.When this alignment films comprises described photoreactive polymer, can show with the interaction of liquid crystal molecule excellently, can effectively carry out light orientation thus.
Above-mentioned alignment films or liquid crystal retardation film are also applicable to realizing in the optical film or optical filter of stereopsis.
In addition, provide according to still another embodiment of the invention a kind of indicating meter that comprises described alignment films.This indicating meter can be liquid-crystal display or dimensional image display etc., described liquid-crystal display comprises for making the alignment films of liquid crystal aligning, and in described dimensional image display, described alignment films is included in for realizing optical film or the wave filter of stereopsis.The structure of these display elements is except comprising described photoreactive polymer and alignment films, and other structures are identical with conventional element, and therefore description is omitted.
Below, for contributing to understand the present invention, enumerate preferred embodiment and describe.But following embodiment is just for exemplifying explanation the present invention, and the present invention not limits to this.
In addition,, in following examples, relate to and all use standard Shu Lunke technology (standard Schlenk technique) or dry box method (dry box method) to be implemented to all operations of the compound of air or water sensitive.Nucleus magnetic resonance (NMR) spectrum is by being used Brooker 300 spectrometers (Bruker 300spectrometer) to obtain, now 1h NMR under 300MHz, and 13c NMR detects respectively under 75MHz.The molecular weight and molecualr weight distribution of open loop hydrogenation polymkeric substance is by using GPC (gel permeation chromato graphy) to measure, now using polystyrene (poly styrene) sample as standard.
Toluene is formed by potassium/benzophenone (potassium/benzophenone) distillatory refining, and methylene dichloride is by CaH 2distillatory refining forms.
preparation example 1:
preparation
Will be by compound (the 116.2g representing, 0.43mol, Fw=270.26), EDCI (N-(3-dimethylaminopropyl)-N '-carbodiimide hydrochloride (N-(3-dimethylaminopropyl)-N '-ethylcarbodiimide hydrochloride), 206g, 1.08mol), DMAP (N, N-Dimethylamino pyridine, 10.5g, 0.09mol) put into after flask, add 1500mlCH 2cl 2.Add DIPEA (diisopropylethylamine, 225ml, 1.29mol), 5-norbornylene-2-methyl alcohol (106.8g, 0.86mol, Fw=124.18) afterwards, at room temperature stir 20 hours.After reaction finishes, add water, and after extracting organic layer, with salt solution, clean organic layer.With filtering after dried over mgso organic layer, by column chromatography (cloumn chromatography) (EA: Hex=1: 7) obtain 74.5g titled reference compound (yield: 46%, Fw=376.43).Purity (GC) is 98%.
1H-NMR(300MHz，CDCl3)：δ7.90-7.71(m，5H)，7.64(d，2H)，7.22-7.14(m，2H)，6.55(d，1H)，6.17-5.98(m，2H)，4.10-3.76(m，2H)，2.94-2.75(m，2H)，2.45(m，1H)，1.91-1.83(m，1H)，1.48-1.16(m，2H)，0.59(m，1H)。
preparation example 2:
preparation
Will be by compound (the 116.2g representing, 0.43mol, Fw=270.29), EDCI (N-(3-dimethylaminopropyl)-N '-carbodiimide hydrochloride, 206g, 1.08mol), DMAP (N, N-Dimethylamino pyridine, 10.5g, 0.09mol) put into after flask, add 1500mlCH 2cl 2.Add DIPEA (diisopropylethylamine, 225ml, 1.29mol), 5-norbornylene-2-methyl alcohol (106.8g, 0.86mol, Fw=124.18) afterwards, at room temperature stir 20 hours.After reaction finishes, add water, and after extracting organic layer, with salt solution, clean organic layer.With filtering after dried over mgso organic layer, by column chromatography (EA: Hex=1: 7) obtain 84.2g titled reference compound (yield: 52%, Fw=376.46).Purity (GC) is 98%.
1H-NMR(300MHz，CDCl3)：δ7.71-7.66(m，3H)，7.22-7.14(m，4H)，7.02(s，2H)，6.45(d，1H)，6.18-5.98(m，2H)，4.10-3.75(m，2H)，3.82(s，3H)，2.94-2.75(m，2H)，2.45(m，1H)，1.91-1.83(m，1H)，1.48-1.15(m，2H)，0.59(m，1H)。
preparation example 3:
preparation
Will be by compound (the 9.15g representing, 32.4mmol, Fw=282.30), 5-norbornylene-2-methyl alcohol (4.82g, 38.9mmol, Fw=124.18), hydroxide zirconium acetate (zirconium acetate hydroxide) (0.1g, 1 % by weight) and after 30ml dimethylbenzene (xylene) puts into flask, under the nitrogen environment of 180 ℃, implement azeotropic and reflux approximately 24 hours.After reaction, cool the temperature to room temperature, and add ethyl acetate 100 volume %.With 1 mole hydrochloride, extract, and water cleans one time again.With magnesium sulfate, be dried and remove after solvent, obtain high viscosity fluent meterial.By column chromatography (EA: Hex=1: 10) obtain 8.05g titled reference compound (casting yield: 64%, Fw=388.47).Purity (GC) is 98%.
1H-NMR(300MHz，CDCl3)：δ7.84-7.71(m，5H)，7.35(d，2H)，7.23-7.14(m，2H)，6.55(d，1H)，6.17-5.98(m，2H)，4.10-3.76(m，2H)，2.94-2.75(m，2H)，2.45(m，1H)，2.22(s，3H)，1.91-1.83(m，1H)，1.48-1.16(m，2H)，0.59(m，1H)。
preparation example 4:
preparation
Will be by compound (the 9.15g representing, 34.1mmol, Fw=268.27), 5-norbornylene-2-propyl alcohol (4.82g, 31.7mmol, Fw=152.24), hydroxide zirconium acetate (0.1g, 1 % by weight) and 30ml dimethylbenzene put into after flask, under the nitrogen environment of 180 ℃, implement azeotropic and reflux approximately 24 hours.After reaction, cool the temperature to room temperature, and add ethyl acetate 100 volume %.With 1 mole hydrochloride, extract, and water cleans one time again.With magnesium sulfate, organic layer is dried and is removed after solvent, obtain high viscosity fluent meterial.By column chromatography (EA: Hex=1: 10) obtain 9.47g titled reference compound (yield: 69%, Fw=402.49).Purity (GC) is 97.5%.
1H-NMR(300MHz，CDCl 3)：δ7.84-7.71(m，5H)，7.35(d，2H)，7.23-7.14(m，2H)，6.55(d，1H)，6.17-5.98(m，2H)，5.0-4.9(m，2H)，2.94-2.75(m，2H)，2.45(m，1H)，1.91-1.83(m，1H)，1.48-1.16(m，2H)，0.59(m，1H)。
embodiment 1:
polymerization
In 250ml Shu Lunke (schlenk) flask, add the 1.13g (3mmol.Fw=376.43) as monomer with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexylphospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 1.0g polymkeric substance (Mw=170,000, PDI=3.2, yield=88%) that obtains for 24 hours of the temperature of 60 ℃.
embodiment 2:
polymerization
In 250ml Shu Lunke flask, add the 3.0g (6.69mmol) as monomer with the 6ml toluene by solvent refined.In this flask, as catalyzer, add the 0.62mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 0.71mg tri-ring ethyl phosphines (tricyclohexylphospine), as promotor, add 0.60mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 2.6g polymkeric substance (Mw=124,000, PDI=2.9, yield=87%) that obtains for 24 hours of the temperature of 60 ℃.
embodiment 3:
polymerization
In 250ml Shu Lunke flask, add the 1.17g (3mmol) as monomer with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexylphospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 0.89g polymkeric substance (Mw=103,000, PDI=3.6, yield=79%) that obtains for 24 hours of the temperature of 60 ℃.
embodiment 4:
polymerization
In 250ml Shu Lunke flask, add the 1.2g (3mmol, Fw=402.49) as monomer with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexylphospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 1.01g polymkeric substance (Mw=143,000, PDI=3.4, yield=84%) that obtains for 24 hours of the temperature of 60 ℃.
embodiment 5:the preparation of the photoreactive polymer based on ring-opening polymerization and hydrogenation reaction
Under Ar atmosphere, in 250ml Shu Lunke flask, add after 6.20g (50mmol) 5-norbornylene-2-methyl alcohol, then add the 34g toluene with solution scouring.This flask is remained under the state of 80 ℃ of polymerization temperatures, first add 11.4mg (1.0mmol) triethyl aluminum (triethylaluminum) as promotor.Then, the ratio with 1: 3 is mixed with to tungsten hexachloride (WCl 8) and ethanol, the 1ml toluene solution (WCl of 0.01 mole (mol/L) 8: 0.01mmol, ethanol: 0.03mmol) add in flask.Finally add after 0.84g (7.5mmol) the 1-octene as molecular weight regulator, at 80 ℃ of temperature, stirring reaction is 18 hours.After reaction finishes, in polymer fluid, splash into a small amount of polymerization terminator EVE (ethylvinyl ether), and stir 5 minutes.
Described polymer fluid is transferred in 300mL high-pressure reactor, added 0.06ml triethyl aluminum (TEA).Then, add after 0.50g Grace Raney's nickel (grace raney Nickel (slurry phase in water)), hydrogen pressure remained on to 80atm, and at 150 ℃ of temperature stirring reaction 2 hours.After reaction finishes, polymer fluid is splashed into and in acetone, precipitates rear filtration, and in 70 ℃ of vacuum drying ovens dry 15 hours.Its result, obtain 5-norbornylene-2-methyl alcohol of 5.62g open loop hydrogenation polymkeric substance (ring-opened hydrogenated polymer) (yield=90.6%, Mw=69,900, PDI=4.92).
The open loop hydrogenation polymkeric substance (15g that adds described 5-norbornylene-2-methyl alcohol in the 2-wide neck flask (neckflask) of 250ml, 0.121mol), triethylamine (Aldrich, 61.2g, 0.605mol), after the THF of 50ml, in the ice-water bath of 0 ℃ (ice-water bath), stir.Will be by 4-benzoyl cinnamyl chloride (4-benzoyl cinnamoyl the chloride) (36.0g representing; 0.133mol; Fw=270.72) be dissolved in the THF of 60ml, with adding flask (additional flask), add at leisure afterwards.After 10 minutes, temperature of charge is increased to room temperature, then stirs 18 hours.With ethyl acetate diluting soln and after transferring to separating funnel, water and NaHCO 3clean for several times, then reaction solution is splashed into and in acetone, precipitate and filter, in 70 ℃ of vacuum drying ovens, be dried 15 hours (yields: 93%).Its result, makes 5-norbornylene-2-methyl-4 '-benzoyl styracin (5-norbornene-2-methyl-4 '-benzoyl cinnamate) open loop hydrogenation polymkeric substance.
embodiment 6:
and polymerization
In 250ml Shu Lunke flask, add the 0.34g (1.2mmol, Fw=284.36) as monomer 0.903g (2.4mmol, Fw=376.43) with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexyl phospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 1.07g polymkeric substance (Mw=130,000, PDI=4.2, yield=86%) that obtains for 24 hours of the temperature of 60 ℃.
embodiment 7:
and polymerization
In 250ml Shu Lunke flask, add the 0.41g (1.2mmol, Fw=344.41) as monomer 0.903g (2.4mmol, Fw=376.43) with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexyl phospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 1.06g polymkeric substance (Mw=80,000, PDI=3.6, yield=81%) that obtains for 24 hours of the temperature of 60 ℃.
comparative example 1: polymerization
In 250ml Shu Lunke flask, add the 0.251g (0.6mmol, Fw=254.33) as monomer with the 3ml toluene by solvent refined.In this flask, as catalyzer, add the 6.73mg Pd (OAc) that is dissolved in 1ml methylene dichloride 2with 7.76mg tri-ring ethyl phosphines (tricyclohexyl phospine), as promotor, add 6.53mg dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (dimethylanilinium tetrakiss (pentafluorophenyl) borate), and at 90 ℃ stirring reaction 18 hours.
React after 18 hours, described reactant is put into excessive ethanol and obtain white polymer throw out.With glass funnel, filter this throw out with collected polymer, by the polymkeric substance of collecting in vacuum drying oven with the dry 0.99g polymkeric substance (Mw=130,000, PDI=4.2, casting yield=86%) that obtains for 24 hours of the temperature of 60 ℃.
preparation example 5: the preparation of liquid crystal film
Use respectively described embodiment 1 and 2 and comparative example 1 in synthetic photoreactive polymer, by following process, manufacture liquid crystal film.First, concentration by described photoreactive polymer with 2 % by weight is dissolved in c-pentanone (c-pentanone) solvent, and by rolling method, to be applied to thickness be polyethylene terephthalate (polyethylene the terephthalate) (trade(brand)name: SH71 of 80 microns, the production of Korea S SKC company) on substrate, its dried thickness is reached afterwards, in 80 ℃ of baking ovens, heat 3 minutes, to remove the inner solvent of filming, and then formation is filmed.
It is 200mW/cm that exposure light source adopts intensity 2high voltage mercury lamp, and utilize wiregrating (Wire-grid) polarizer of Moxtek company, to send the UV with the vertical polarisation of film direction, with this UV, irradiate to film and make its orientation 5 seconds, thereby form alignment films.
Then, to be mixed with 95.0 % by weight UV polymerizability cyanobiphenyl acrylate (cyanobiphenyl acrylate) and be dissolved in toluene solvant as the solid substance of gorgeous good solid (irgacure) 907 (production of Switzerland Ciba-Geigy company) of 5.0 % by weight of light trigger, and make liquid crystal content reach 25 weight parts with respect to the liquid crystal solution of 100 weight parts, thereby prepare polymerisable reactive liquid crystalline solution.
By rolling method, the liquid crystal solution of preparation is coated on described established optical alignment film, and makes its dried thickness reach 1 μ m, with dry 2 minutes of the temperature of 80 ℃, liquid crystal molecule is orientated afterwards.By intensity, be 200mW/cm 2high voltage mercury lamp as the unpolarized UV of light source, irradiate the liquid crystal film being orientated, with the fixing state of orientation of liquid crystal, thereby manufacture phase retardation film.
For the orientation of the above-mentioned phase retardation film of making, with printing opacity instrument (transmittance), detect light leak between Polarizer to compare, and use Axoscan (production of Axomatrix company) to detect quantitative phase difference value.
< test example 1>
the evaluation of orientation (evaluation of light leak degree)
For the orientation evaluation of alignment films, with polarizing microscope, between two Polarizers (polarizer) of arranged perpendicular, observed the liquid crystal retardation film that uses the photoreactive polymer of embodiment 1,2 and comparative example 1 to make in preparation example 5.Orientation is expressed as 1～5 integer, and more approaching 5, to be evaluated as orientation more excellent.
For transmittance, polyethylene terephthalate (trade(brand)name: SH71 with 80 microns of thickness, Korea S SKC company produces) as benchmark, between the Polarizer of arranged perpendicular, placing after described liquid crystal retardation film, with polarized light microscope observing irradiate the degree of light transmission Polarizer and phase retardation film, with this, detect light leak degree.This orientation evaluation result based on light leak degree detecting and the detected result of described phase difference value are illustrated in table 1.
[table 1]
*while carrying out described orientation evaluation, it is 100mJ/cm that UV solidifies light quantity 2remain unchanged, after curing each alignment films, carry out liquid crystal aligning.
*while detecting described phase difference value, utilize light that wavelength region is 550nm to detect the phase difference value of pellicular front direction.
Known with reference to described table 1, no matter the phase retardation film forming with the polymkeric substance of embodiment 1 and 2, inject the wavelength of light for how many, and its differently-oriented directivity evenly shows excellent orientation, and phase difference value is 129nm and 125nm in pellicular front, the anisotropy based on liquid crystal is comparatively desirable.
In contrast to this, the phase retardation film of manufacturing with the polymkeric substance of comparative example 1, orientation reduces and the differently-oriented directivity of liquid crystal is shaken, and compares with using the situation of embodiment 1 and 2, although there is identical thickness of liquid crystal, because phase difference value less anisotropy is unsatisfactory.

Claims (9)

1. a cyclic olefins with the photoreactive group being represented by following Chemical formula 1,
[Chemical formula 1]
In described Chemical formula 1,
Q is 0,
At least one in R1, R2, R3 and R4 is the group being represented by following Chemical formula 1 a,
Except the group being represented by Chemical formula 1 a, remaining R1～R4 is identical or different, and respectively independently selected from hydrogen; With the carbonatoms straight or branched type alkyl that is 1～6;
[Chemical formula 1 a]
In described Chemical formula 1 a,
A be selected from oxygen, carbonyl ,-(O=) C-O-and-O-C (=O)-,
B is singly-bound or oxygen,
R9 is selected from the alkylidene group that singly-bound and carbonatoms are 1～6,
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～12;
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～12;
R10 is selected from: hydrogen; Halogen; Carbonatoms is 1～20 straight or branched type alkyl; With the carbonatoms alkoxyl group that is 1～20.
2. a photoreactive polymer that comprises the repeating unit being represented by following Chemical formula 2 a or 2b,
In described Chemical formula 2 a and 2b, distinguish independently,
M is 50～5000,
Q is 0,
R1, R2, in R3 and R4, at least one is the group being represented by following Chemical formula 1 a,
Except the group being represented by Chemical formula 1 a, remaining R1～R4 is identical or different, and respectively independently selected from hydrogen; With the carbonatoms straight or branched type alkyl that is 1～6;
[Chemical formula 1 a]
In described Chemical formula 1 a,
A be selected from oxygen, carbonyl ,-(O=) C-O-and-O-C (=O)-,
B is singly-bound or oxygen,
R9 is selected from the alkylidene group that singly-bound and carbonatoms are 1～6,
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～12;
the arylidene that the carbonatoms replacing at least one functional group that is not substituted or is selected from halogen, cyano group and nitro is 6～12;
R10 is selected from hydrogen; Halogen; Carbonatoms is 1～20 straight or branched type alkyl; With the carbonatoms alkoxyl group that is 1～20.
3. photoreactive polymer according to claim 2, it has 10,000～1,000,000 weight-average molecular weight.
4. the preparation method of a photoreactive polymer claimed in claim 2, it comprises step: exist and comprise under the condition that contains the 10th pre-catalyst of group 4 transition metal and the catalyst composition of promotor, the monomer that addition polymerization is represented by Chemical formula 1, to form the repeating unit being represented by Chemical formula 2 a
[Chemical formula 1]
In described Chemical formula 1, q, R1, R2, R3 and R4 as in claim 2 define.
5. the preparation method of a photoreactive polymer claimed in claim 2, it comprises step: exist and comprise under the condition that contains the 4th family, the 6th family or the 8th pre-catalyst of group 4 transition metal and the catalyst composition of promotor, the monomer that ring-opening polymerization is represented by Chemical formula 1, to form the repeating unit being represented by Chemical formula 2 b
[Chemical formula 1]
In described Chemical formula 1, q, R1, R2, R3 and R4 as in claim 2 define.
6. the preparation method of photoreactive polymer according to claim 5, in wherein said ring-opening polymerization step, makes the two keys in norbornylene ring that the monomer of described Chemical formula 1 comprises be carried out ring-opening polymerization by hydrogenation.
7. an alignment films that comprises the photoreactive polymer described in claim 2 or 3.
8. one kind comprises alignment films claimed in claim 7 and the liquid crystal retardation film that is positioned at the liquid crystal layer in described alignment films.
9. an indicating meter that comprises alignment films claimed in claim 7.
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